Archaeological research is increasingly relying on materials characterization protocols to provide information on artefacts and remains. Indeed, analytical results are fundamental to draw meaningful conclusions as concerns: raw materials procurement and provenance; technological advancement levels; commercial exchanges and societal aspects. Experimental measurements are done both ex-situ, by extracting small portions of material from the analyzed object, and in-situ, exploiting non-destructive techniques, that can probe the material without sampling or alteration. This approach is also interesting for ex-situ analyses, as it opens the possibility of combining different experimental techniques on the very same sample, even if a limited amount of material is available. In the present paper, we highlight the possibilities offered by the combined use of Raman and X-ray fluorescence (XRF) spectroscopy of Archaeological specimens. These two techniques are non-destructive and provide information on the elemental composition as well as on the structure of the investigated materials. The combined analytical and structural information is particularly important when dealing with natural materials, like garnets in the present study, commonly featuring intrinsic fluctuations in the chemical composition. Moreover, the approach can smoothly assess the actual origin of materials that can be of natural, like minerals, or anthropogenic, like glasses, origin. As a case study, we critically discuss the results obtained on two brooches, decorated with garnets and glasses, belonging to the Longobard culture in the North-Eastern Italian regions. The combination of the analytical data, from XRF spectroscopy, and of the structural ones, from Raman spectroscopy, provide indications on the composition of the base alloys and provenance of the mentioned stones.



